US4151143A - Surfactant-free polymer emulsion coating composition and method for preparing same - Google Patents

Surfactant-free polymer emulsion coating composition and method for preparing same Download PDF

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US4151143A
US4151143A US05/826,207 US82620777A US4151143A US 4151143 A US4151143 A US 4151143A US 82620777 A US82620777 A US 82620777A US 4151143 A US4151143 A US 4151143A
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stage
mixture
polymer
polymerizable monomers
water
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Werner J. Blank
Ralph E. Layman
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Wyeth Holdings LLC
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American Cyanamid Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters

Definitions

  • This invention relates to coating compositions. More particularly, it relates to novel surfactant-free polymer emulsions having highly superior properties for use as film coatings for metal and glass surfaces and to a method for preparing these emulsions.
  • the water-soluble acrylic polymers used in coatings are of relatively low average molecular weights, i.e. from about 3,000 up to about 50,000.
  • high levels of cross-linking agent have to be used.
  • significant levels of amine and cosolvent have to be used in the coating compositions so that the amount of amine and solvent emitted from the coatings during baking is considerable.
  • the water-soluble compositions while having advantages, such as ease of application and uniformity and high gloss in the cured films, are still less flexible than desired and lack some desirable properties such as good water and detergent resistance.
  • the well-known emulsion-type coating compositions in which the polymers are of relatively high molecular weight, do not require such large amounts of cross-linking agents as do the water-soluble polymer compositions and so provide cured films of high flexibility and good durability and mechanical resistance properties.
  • the emulsion polymer systems present other problems, such as poor wetting of the metal substrate and tendency of the films to crater. Also, because they form a film by the coalescence of the emulsion particles they often give low gloss or a mudcaking effect.
  • the emulsion systems also require a relatively large amount of cosolvent in order to reduce blistering.
  • emulsions The main problem with emulsions, however, is the presence therein of surfactants which are required to form a stable emulsion and also to overcome the wetting and adherency problems of the emulsions. Unfortunately, the surfactants remain in the film after cross-linking and adversely affect the water and corrosion resistance of the film as well as the adhesion of the coating to the metal surface.
  • the preparation of the emulsion polymer of the invention is carried out in two stages.
  • stage II monomers there is added to the dispersion of stage I a blend of partially water-soluble and partially water-insoluble monomers, hereinafter referred to as the stage II monomers, together with a free radical initiator.
  • the stage II monomers polymerize in the stage I dispersion, which results in grafting and the formation of a very stable emulsion without the presence of any added surfactant.
  • the grafting of the stage II monomers onto the stage I polymer increases the overall molecular weight of the system and also produces an emulsion of excellent mechanical stability.
  • the process of the invention requires a water-solubilizing group, such as carboxyl-containing monomer, only in the stage I polymer, the total content of water-solubilizing sites in the stage I and stage II monomers can be decreased. This decrease in carboxyl groups in the total of stage I and stage II monomers permits a significant reduction in the amount of neutralizing amine required.
  • the stage I and stage II monomers are initially combined (in a single stage polymerization process) to make a solution polymer, the resulting dispersion is either very unstable or no dispersion is formed at all.
  • stage I of the process a mixture of monomers composed of about 3-15% of at least one polymerizable carboxylic acid or anhydride and at least one other polymerizable monomer is used.
  • Acrylic acid or anhydride and maleic acid or anhydride are preferred as the carboxylic acid or anhydride, although other acids or anhydrides may be used, for example, ⁇ -methacrylic acid or anhydride and the C 1 -C 8 alkyl half esters of maleic acid, such as the 2-ethylhexyl ester.
  • the other polymerizable monomer may suitably be an acrylic acid ester, such as methyl, ethyl, propyl, butyl, or 2-ethylhexyl acrylates or methacrylates, 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate and ethylhexyl acrylate.
  • acrylic acid ester such as methyl, ethyl, propyl, butyl, or 2-ethylhexyl acrylates or methacrylates, 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate and ethylhexyl acrylate.
  • styrene, vinyl toluene or acrylamide may be used along with or instead of the acrylic esters in the monomer mixture.
  • amines may be used in stage I of the process.
  • dimethylethanol amine is generally preferred, other amines such as diethanol amine, diethyl ethanol amine, butyl amine, 2-amino, 2-methyl-1-propanol, tris hydroxymethyl amino methane and morpholine are suitable amines.
  • the stage II monomer mixture contains no polymerizable acid, but is composed of monomers such as methyl, ethyl, propyl and butyl acrylates or methacrylates, beta-hydroxyethyl and beta-hydroxypropyl acrylate or methacrylate, acrylamide and isobutoxymethyl acrylamide. Also, acrylonitrile and styrene may be used.
  • the preferred monomer mixture is composed of 2-hydroxyethyl acrylate, butyl acrylate, and methyl methacrylate.
  • the proportions of the Stage I and Stage II monomer mixtures suitable for use in the process of the invention are such that either mixture can comprise from about 20 to about 80 weight percent, preferably about 50 weight percent, of the total of the two mixtures.
  • the present invention is a two-stage method for preparing a surfactant-free emulsion product which comprises, in a first stage, (1) forming a mixture of polymerizable monomers comprising, by weight from about 3 to about 15% of a carboxylic acid or anhydride selected from the group consisting of acrylic, methacrylic and maleic acid and their anhydrides and the C 1 -C 8 alkyl half esters of maleic acid, from about 30 to about 97% of a C 1 -C 8 alkyl acrylate or C 1 -C 8 alkyl methacrylate, from 0 to about 25% of a C 2 -C 4 hydroxy alkyl ester of a carboxylic acid or acrylamide or methacrylamide and from 0 to about 35% styrene, (2) polymerizing said mixture in the presence of a polymerization catalyst, a suitable solvent, and optionally, a molecular weight regulator to form a polymer having an average molecular weight of from about 3000 to about
  • the mixture of polymerizable monomers in said first stage comprises from about 5-10% acrylic acid about 5-15% of 2-hydroxyethyl acrylate and about 35-50% butyl acrylate and about 25-55% methyl methacrylate and the mixture of polymerizable monomers in said second stage comprises about 1-10% of 2-hydroxyethyl acrylate, about 35-50% butyl acrylate and about 25-55% methylmethacrylate.
  • the mixture of polymerizable monomers in said first stage may comprise about 5-10acrylic acid, about 35-50% butyl acrylate, about 25-55% methylmethacrylate and about 10-30% styrene and the mixture of polymerizable monomers in said second stage comprises about 5-10% of 2-hydroxyethyl acrylate, about 35-50% butyl acrylate and about 25-55% methyl acrylate.
  • the second stage also contains 10-30% styrene.
  • the mixture of polymerizable monomers in said first stage comprises about 5-10% acrylic acid, about 35-50% butyl acrylate, about 25-55% methylmethacrylate and about 5-15% acrylamide and the mixture of polymerizable monomers in said second stage comprises about 5-10% 2-hydroxyethyl acrylate, about 35-50% butyl acrylate and about 25-35% methyl acrylate.
  • the propylene glycol and 2-ethoxy ethanol (components 6 and 7) were charged to a 3 liter 4-necked flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser. Air in the flask was displaced by nitrogen and the contents heated to reflux temperature (130°-135° C.). Components 1-5 were mixed together, and when the peroxide was completely dissolved the mixture was added at a uniform rate to the 4-necked flask over a 2 hour period during which the temperature gradually rose to 155° C. After holding at this temperature for two hours, the batch was cooled to 100° C. and 2.4% wt. of dimethyl amino ethanol (DMAE) was stirred in to form an amine salt of the polymer.
  • DMAE dimethyl amino ethanol
  • reaction mixture After cooling to 80° C. a 500-gram portion of the reaction mixture was transferred to a steel beaker. With the aid of a high speed stirrer having a blade tip speed of approx. 800 ft./min., 600 gms. of water at 70° C. were added slowly to the mixture, thereby producing a thin milky dispersion having a pH of 7.2, a solids content of 42%, and viscosity of 200 centipoises. Cooling to room temperature was done in a water bath.
  • a monomer mix composed of 7 gms. of 2-hydroxy ethyl acrylate, 41 gms. of butyl acrylate and 53 gms. of methyl methacrylate was sparged with nitrogen and then slowly added to a mixture of 240 gms. of the emulsion prepared in Stage I and 100 gms. of de-airated water in a flask equipped with stirrer, gas inlet tube, thermometer and reflux condenser. A blanket of nitrogen was maintained over the liquid in the flask. The addition of the monomer mix made the mixture thicker than the initial Stage I emulsion. Next, 0.4 gm. of ammonium persulfate (98%) was added to 12 gms.
  • the pH of another portion of the copolymer emulsion was raised to about 8 by addition of a 20% solution of dimethyl amino ethanol (DMAE).
  • DMAE dimethyl amino ethanol
  • HMMM hexakismethoxymethyl melamine
  • a 0.003" wet film drawn down on sheet aluminum was baked 1 min. at 500° F. to yield a clear, glossy, hard film. Pencil hardness was F and reverse impact resistance was 40 inch pounds.
  • Example 2 The procedure was similar to Example 1, except that the monomer mixture used was 7% acrylic acid, 6% ⁇ -hydroxy ethyl acrylate, 41% butyl acrylate and 46% methyl methacrylate. A dispersion in water was made just as in Example 1.
  • a copolymer emulsion using the emulsion polymer of Stage I of Example 2 was prepared similarly to that of Stage II of Example 1 except that the added monomer mixture was composed of 1% ⁇ -hydroxyethyl acrylate, 49% butyl acrylate and 50% methyl methacrylate. Final solids was 44%, pH, 7.2 and viscosity, 115 centipoises. The compatability of the stage I and stage II polymers is shown by the fact that when a thin film of this product was air-dried and baked, a clear glossy film was formed.
  • the monomer mixture (135 gms.) was composed of 7% ⁇ -hydroxyethyl acrylate, 46% butyl acrylate and 47% methyl methacrylate.
  • the procedure involved stirring a solution of 2.5 gms. of DMAE in 145 gms. of de-airated water into the emulsion of stage I, then stirring in the mixture of monomers. Finally, 0.4 gms. of ammonium persulfate in 18 grams of water were added dropwise. Mild heating and stirring were then applied until the flask contents reached 50° C. The heat was then removed and the contents held at 50°-55° C. for four hours.
  • the procedure here was the same as that for Stage I of Example 1, except that the monomer mixture used was 7% acrylic acid, 30% styrene, 27% methyl methacrylate and 36% butyl acrylate, and the propylene glycol was replaced by ethoxy ethanol.
  • a copolymer emulsion using the emulsion of Stage I above was prepared in a fashion similar to that of Stage II, Example 1, except that the added monomer mixture was 7.5% ⁇ -hydroxyethyl acrylate, 27.5% styrene, 28% methyl methacrylate and 37% butyl acrylate, and the pH of the emulsion was adjusted with DMAE to 8.5 at the start of the copolymerization.
  • the finished copolymer emulsion had a viscosity of 140 centipoises, a pH of 7.1 and a solids content of 43.4%.
  • this product yielded films on aluminum which baked in 30' at 250° F. to hard, glossy, solvent-resistant coatings.
  • This copolymer emulsion was compounded with 11% of a polymeric partially methylated melamine-formaldehyde resin (80% concentration in water) to yield a clear baking enamel of 42% solids.
  • a polymeric partially methylated melamine-formaldehyde resin 80% concentration in water
  • the cured coating had good gloss, clarity, flow and color, and no crater or dimple defects.
  • Reverse impact was 60 in. lbs., and MEK resistance was in excess of 200 rubs.
  • the clear baking enamels of the foregoing examples may be pigmented with titanium dioxide to yield white high gloss enamels having utility as coatings for sheet metal, coiled metal, and fabricated metal items.
  • the product was a thin liquid of pH 6.6, having a viscosity of 65 centipoises, and a solids content of 43.5%.
  • the pH was adjusted up to 7.5 using dilute DMAE and then a film was cast on glass. After the film air-dried 30' it was clear, hard and glossy.
  • Example 2 An emulsion polymer was made as in Example 1 using maleic anhydride instead of acrylic acid.
  • the monomer mixture had the following components: maleic anhydride, 100 gms., styrene, 140 gms., butyl acrylate, 560 gms., methyl methacrylate, 600 gms., and dicumyl peroxide, 28 gms.
  • maleic anhydride 100 gms., styrene, 140 gms., butyl acrylate, 560 gms., methyl methacrylate, 600 gms., and dicumyl peroxide, 28 gms.
  • the mixture was added, over a 2 hr. period, to 125 parts of para-cymene at a temperature of 140°-160° C. and the whole held at 160° C. for two hours. After cooling to 140° C., there was added 90 gms.
  • the solids was 40%, the viscosity 100 centipoises and the pH 6.8. The latter value was raised to 7.1 by addition of some dilute DMAE.
  • a film was cast, on clear glass, and after air-drying several hours the film was smooth, hard, clear, and glossy. The film was baked 10 minutes at 300° F., cooled to room temperature, and then immersed in water. It did not blister or turn white within a 3 day period.
  • a monomer blend consisting of 14 parts by weight of 2-hydroxyethyl acrylate, 15.5 parts acrylic acid, 93.5 parts butylacrylate, 108 parts methylmethacrylate, 3.35 parts n-dodecyl mercaptan and 4.45 parts dicumyl peroxide was fed over a 21/2 hour period into a mixture of 10 parts 2-ethoxyethanol and 10 parts propylene glycol in a reactor eqipped with a stirrer and reflux condenser. After the monomer addition was complete, the temperature of the reaction mixture was 148° C. and was maintained at that level for an additional hour to insure complete monomer conversion.
  • the batch was then cooled to 90° C. and 6 parts of dimethylaminoethanol (DMAE) added. Then, under high speed agitation, 290 parts of water were slowly added without permitting the batch temperature to fall below 70° C.
  • DMAE dimethylaminoethanol
  • the total monomer blend (Stage I and Stage II monomers) contained 3.3% acrylic acid, 3.5% hydroxyethylacrylate, 44.6% butylacrylate and 48.6% methylmethacrylate.
  • Gell phase analysis of the stage I polymer dispersion showed an average molecular weight of about 10,000.
  • the molecular weight fraction of 10,000 had decreased to about 32%, while about 39% had an average molecular weight of about 500,000 and about 29% had a molecular weight greater than 2,000,000. This reduction in the 10,000 molecular weight fraction from 50% to 32% is a clear indication that a significant amount of grafting of the Stage II monomers onto the polymers formed from the stage I monomers had taken place.
  • the emulsion prepared above was formulated into a water-reducible coating using hexamethoxymethyl melamine (Formulation A) or a partially methylated melamine formaldehyde (Formulation B) as cross-linking agent. Excellent glossy films were obtained which were uniformly hard and flexible. The pertinent data are shown in Table II. The enamel solids of 56.7% and 59.7% obtained with Formulations A and B, respectively, is very high for a water-borne coating system. Formulation B cures adequately at 250° F. giving an excellent gloss of 94 (60°) and 71 (20°).
  • HMMM as a cross-linking agent (Formulation A) requires a higher baking temperature, but results in a more flexible coating.
  • the emulsion was also formulated into a coil-coating formulation.
  • the pertinent data are shown in Table III.
  • Formulation A was modified with 10% and 20% of HMMM as a cross-linking agent.
  • HMMM as a cross-linking agent.
  • the excellent flexibility of T-2 bend is obtained.
  • Even increasing the level of amino resin to 15% produces a T-3 bend.
  • a solution polymer prepared with the same polymer composition as in Example 8 gives a flexibility of less than T-4.
  • a water-soluble resin was prepared according to the procedure of stage I, Example 8, except that the monomer blend was adjusted to give the closest approximation in composition to the total monomer blend (stage I and II monomers) of Example 8. Thus, all of the monomers were polymerized at once, rather than in two stages. To achieve water-solubility, the acrylic acid content had to be raised to 9%, using 45% butylacrylate and 46% methylmethacrylate as comonomers. The resulting polymer solution in 2-ethoxyethanol had a viscosity of Z-6 on the Gardner-Holdt scale and a solids content of 75%. The average molecular weight of the blend was about 10,000.
  • Example 9 Compared to Formulation A of Example 8, the water-reducible system of Example 9 contains about 5.3 times more solvent.
  • a formulated coating with the water-soluble resin of Example 9 has significant lower application solids than that of Example 8.
  • a wet film thickness 3.1 mil would have to be applied with the Formulation C using the resin of Example 9 compared to a wet film thickness of 2.2 for the same dry film thickness with the resin from Example 8.
  • the likelyhood of sagging, tear formation in spray applying a formulation on vertical surfaces using the resin of Example 9, is therefore, significantly increased over the same formulation in Example 8.
  • the gloss obtained with Formulation C, Example 9, surprisingly is lower than that of Example 8, with the exception of the 20° gloss at a baking temperature of 20 minutes at 300° F.
  • Example 9 The lower application solids in Example 9 (45%) compared to Formulation A of Example 8 (56.7%) also causes increased problems in flash-off.
  • An emulsion polymer was prepared by conventional procedure, i.e. polymerizing the total monomer composition (the monomers of stage I plus the monomers of Stage II) of Example 8 all at once.
  • Aerosol A-102 a sulfosuccinate
  • the resulting acrylic emulsion polymer was pigmented and formulated the same as Formulation A, Example 8. Because of the poor wetting characteristics and poor stability of the emulsion, a water-soluble resin of the composition in Example 9 was used as a wetting agent for the pigment.
  • the film of the Formulation A, Example 8, emulsion (no surfactant) is also clearly superior in water resistance to the film of Example 10 containing a conventional surfactant and is also superior to the surfactant-free polymer of Example 9 which contains higher levels of cross-linking agent.
  • Example 10 The addition of the surfactant used in Example 10 to the emulsion Formulation A of Example 8 produces similar softening and adhesion problems on water immersion to those shown for Example 10.
  • Example 10 Draw down of the formulation of Example 10 on steel causes yellow staining and flash rusting whereas the systems of Examples 8 and 9 show no such effect.
  • the emulsions of the present invention which contain no added surfactant, exhibit superior film-forming properties to polymer emulsions produced by conventional emulsion polymerization procedures using a regular surfactant.
  • pigmentation of the emulsions is very easy since direct addition of the pigment can be used and the pigment ground in the emulsion.
  • the emulsions show very good wetting of poorly cleaned metal surfaces with no creeping or pinholing occurring in the applied film. Also, the films made with the emulsions of the invention are of high gloss and give no mudcracking.
  • the films provided by the emulsions exhibit excellent moisture resistance showing only a very small loss of hardness and no loss of adhesion in the water immersion test.

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CA000307509A CA1116773A (en) 1977-08-19 1978-07-17 Surfactant-free polymer emulsion coating composition and two-stage method for preparing same
JP10046778A JPS5443286A (en) 1977-08-19 1978-08-19 Twoostage preparation of polymer emulsion product containing no surfaceeactive agent

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